Dichlorovinylthionophosphoric acid ester amides

ABSTRACT

Dichlorovinylthionophosphoric acid ester amides of the formula   in which R is alkyl of 1 to 16 carbon atoms which may be substituted by alkoxy of 1 to 6 carbon atoms, cycloalkyl, cycloalkenyl, cyano, halo or aryl; cycloalkyl; aryl; or alkylaryl, and R1 and R2 each independently is hydrogen; alkyl of 1 to 8 carbon atoms which may be substituted by aryl, cyano or alkoxy; aryl; or alkenyl of 2 to 8 carbon atoms; or together with the nitrogen atom to which they are attached form a heterocyclic ring, WHICH POSSESS INSECTICIDAL, ACARICIDAL, NEMATOCIDAL, RODENTICIDAL, FUNGICIDAL AND BACTERICIDAL PROPERTIES.

United States Patent 1 Sirrenberg et al.

[ DICHLOROVINYLTHIONOPHOSPHORIC ACID ESTER AMIDES [75] Inventors:Wilhelm Sirrenberg, Sprockhovel, l;

Bernard Homeyer, Opladen; Ingeborg Hammann, Cologne; Wilhelm Stendel,Wuppertal-Elberfeld, all of Germany [73] Assignee: BayerAktiengesellschaft,

Leverkusen, Germany 22 Filed: Sept. 30, 1974 2| Appl.No.:5l0,835

Related US. Application Data [63] Continuation-in-part of Ser. No.267,759, June 30,

i972. abandoned.

[ Nov. 4, 1975 Primary ExaminerRichard L. Raymond Attorney, Agent, orFirmBurgess, Dinklage & Sprung 57 ABSTRACT Dichlorovinylthionophosphoricacid ester amides of the formula in which R is alkyl of l to 16 carbonatoms which may be substituted by alkoxy of l to 6 carbon atoms,cycloalkyl, cycloalkenyl, cyano, halo or aryl; cycloalkyl; aryl; oralkylaryl, and R and R each independently is hydrogen; alkyl of 1 to 8carbon atoms which may be substituted by aryl, cyano or alkoxy; aryl; oralkenyl of 2 to 8 carbon atoms; or together with the nitrogen atom towhich they are attached form a heterocyclic rmg, which possessinsecticidal, acaricidal, nematocidal, rodenticidal. fungicidal andbactericidal properties.

7 Claims, No Drawings DICHLOROVINYLTHIONOPHOSPHORIC ACID ESTER AMIDESThis application is a continuation-in-part of Application Ser. No.267,759, filed June 30, [972, now abandoned.

The present invention relates to and has for its objects the provisionof particular new dichlorovinylth ionophosphoric acid ester amides i.e.O(optional]y substituted-alkyl, arylor -cycloalkyl)-N-( unsubstituted-,monoor disubstituted)dichlorovinylthionophosphoric acid ester amides,which possess insecticidal, acaricidal, nematocidal, rodenticidal,fungicidal, and bactericidal properties, active compositions in the formof mixtures of such compounds with solid and liquid dispersible carriervehicles, and methods for producing such compounds and for using suchcompounds in a new way especially for combating pests, e.g. insects,acarids, nematodes, rodents, fungi and bacteria, especially insects,acarids and nematodes, with other and further objects becoming apparentfrom a study of the within specification and accompanying examples.

It is already known from German Published Specification (DAS) 1,083,253that 0,0'dialkyl-O-[2,2- dichlorovinyll-phosphoric acid esters, forexample 0,0-dimethyl-O-{2,2-dichloroviny]l-phosphoric acid ester,(Compound A) possess an insecticidal action.

The present invention provides, as new compounds, thedichlorovinylthionophosphoric acid ester amides of the formula in whichR is alkyl of 1 to 16 carbon atoms which may be substituted by alkoxy of1 to 6 carbon atoms, cycloalkyl, cycloalkenyl, cyano, halo or aryl;cycloalkyl; aryl; or alkylaryl, and R and R, each independently ishydrogen; alkyl of l to 8 carbon atoms which may be substituted by aryl,cyano or alkoxy; aryl; or alkenyl of 2 to 8 carbon atoms; or togetherwith the nitrogen atom to which they are attached form a heterocyclicring.

Surprisingly, the dichlorovinylthionophosphoric acid ester amidesaccording to the invention are distinguished by a considerably betterinsecticidal, especially soil-insecticidal, acaricidal and nematocidalaction than the known 0,0-dialkyl-O-[2,2-dichlorovinyl1- phosphoric acidesters of analogous structure and identical type of action. Thecompounds according to the invention hence represent a genuineenrichment of the art.

Preferably, in the formula (I) above, R is alkyl with l to 12 carbonatoms (for example methyl, ethyl, nor isopropyl, n-, sec-, tert.- orisobutyl, n-, isoor neopentyl, n-hexyl, n-heptyl, n-octyl, Z-ethyIbutyl,2,2-dimethylbutyl, 2-ethylhexyl, 2,2-dimethylhexyl, n-decyl,2,2-dimethyloctyl, n-dodecyl or 2,2-dimethyldecyl),

HNiCHg): Acid'binding agent Cl C=CH-O P 2,2,2-trichloroethyl,l,3-dichloropropy|, 2-chloroethyl, 2-bromoethyl, cyanoethy],cyclopenty], cyclohexyl, cyclopentylmethyl, cyclopentylethyl,cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl,cyclohexen-3-yl-methyl, phenyl, alkylpheny] (for example 4-methyl,4-ethyI-, 4-nor isopropylor 4-tert. -butylphenyl), benzyl, phenethyl,3-phenylpropyl, methoxymethyl, methoxyethyl, methoxypropyl,methoxybutyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl,propoxymethyl, propoxyethyl, propoxypropyl, butoxyethyl or butoxypropyl;and R and R are individually hydrogen, cyanoethyl, benzyl, phenethyl,lower alkyl with l to 4 carbon atoms alkoxyalkyl with l to 4 carbonatoms per alkyl moiety or lower alkenyl with 3 or 4 carbon atoms (forexample propenyl, allyl, buten-I-yl, buten-2-yl or isobutenyl) or,conjointly with the nitrogen atom, form a morpholino, pyrrolidine orpiperidine radical.

A preferred sub-group of compounds is those wherein R, is hydrogen, R ismethyl, isopropyl, isobutyl or sec.-butyl and R is methyl, ethyl, propylor allyl. Of these, especially preferred areO-isobutyl-O-(2,2-dichlorovinyl)-N-methylthionophosphoric acid esteramide,

O-mcthyl-O-(2,2-dichlorovinyl)-N-allyl-thionophosphoric acid esteramide,

O-methyl-O-( 2,2-dichlorovinyl )-N-propyl-thionophosphoric acid esteramide,

O-isopropyl-O-( 2 ,2-dichlorovinyl -N -ethyl-thionophosphoric acid esteramide, and

O-isobutyl-O-(2,2-dichlorovinyl)-N-ethyl-thionophosphoric acid esteramide,

The present invention also provides a process for the preparation of adichlorovinylthionophosphoric acid ester amide of the formula (I) inwhich dichlorovinylthionophosphoric acid ester dichloride of the formulais reacted with a hydroxy compound of the general formula ROH (lll) inwhich R has the meaning stated above, in the presence of an acid-bindingagent to give the corresponding monochloride, which is subsequentlyreacted, optionally without prior isolation, with an amino compound ofthe general formula in which R and R, have the meanings stated above,also in the represented by the following equation:

CI agent (.I HCl (lllal (Va) II z s As examples of the primary andsecondary amines and hydroxy compounds that can be employed in thepreparative process, the following compounds may be mentioned:methylamine, ethylamine, N- or isopropylamine, n-, sec.-, tert.- orisobutylamine, Z-cyanoethylamine, benzylamine, phenethylamine,allylamine, propenylamine, buten-l-ylamine, buten-Z-ylamine orisobutenylamine, also dimethylamine, diethylamine, di isopropylamine,dipropylamine, di-isobutylamine, di-n-butylamine or di-tert.-butylamine,as well as morpholine, pyrolidine or piperidine, and also methyl, ethyl,nand isopropyl, n-, sec.-, tert.- or isobutyl, rl-, isoor neopentyl,n-hexyl, n-heptyl, n-octyl, 2-ethylbutyl, 2,2-dimethylbutyl,Z-ethylhexyl, 2,2-dimethylhexyl, n-decyl, 2,2-dimethyloctyl, n-dodecyl,2,2-dimethyldecyl, 2,2,2-trichloroethyl, 1,3-dichloropropyl,2-chloroethyl, 2-cyanoethyl, cyclopentyl, cyclohexyl, cyclopentylmethyl,cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl,cyclohexylpropyl, cyclohexen-3-yl-methyl, benzyl, phenethyl,3-phenylpropyl, methoxymethyl, methoxyethyl, methoxypropyl,methoxybutyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl,propoxymethyl, propoxyethyl, propoxypropyl, butoxyethyl or butoxypropylalcohol, as well as phenol and p-methylmercaptophenol.

The hydroxy and amino compounds required as the starting materials areknown from the literature and are also easily obtainable on anindustrial scale. O-[2,2- dichlorovinyl]-thionophosphoric acid esterdichloride can be obtained, in accordance with a process that does notform part of the state of the art, from O-[2,2-dichlorovinyl]-phosphoric acid ester dichloride, phosphorus pentasulfideand phosphorus sulfochloride at temperatures between 1 and 160C in thepresence of a solvent.

The preparative process for the compounds of this invention ispreferably carried out with the use of a suitable solvent or diluent.Practically all inert organic solvents can be used for this purpose;especially suitable are aliphatic and aromatic hydrocarbons (which maybe chlorinated), such as benzene, toluene, xylene, petroleum ether,benzine, methylene chloride, chloroform, carbon tetrachloride orchlorobenzene, ethers, for example diethyl ether, dibutyl ether ordioxane, ketones, for example acetone, methyl ethyl ketone, methylisopropyl ketone or methyl isobutyl ketone, and nitriles, such asacetonitrile or propionitrile.

As an acid-binding agent it is possible to use any customary acidacceptor. Alkali carbonates and alkali alcoholates, such as sodium andpotassium carbonate, sodium and potassium methylate and sodium andpotassium ethylate, as well as aliphatic, aromatic and heterocyclicamines, for example triethylamine, dimethylamine, dimethylaniline,dimethylbenzylamine and pyridine, have proved particularly successful.

The reaction temperature can be varied within a fairly wide range. Ingeneral, the reaction is carried out at about 0 to 100C, preferably atabout to 50C. The reaction is generally effected at normal pressure.

Generally, to carry out the process, the reaction of theO-[2,2-dichlorovinyl]-thionophosphoric acid ester dichloride is effectedby dissolving the latter in a suitable solvent or diluent and firstadding to this solution, while stirring and at the indicatedtemperatures, an appropriately cooled mixture of the particular hydroxycompound, acid-binding agent and solvent. Thereafter, the salt-likeprecipitate that has separated out is filtered off and eluted with thesolvent employed. The filtrate is treated dropwise with a mixture of theamino compound, solvent and acid-binding agent, though it is alsopossible to choose the converse sequence, and thereafter the reactionmixture is stirred for some time longer at room temperature. Thereaction mixture is worked up in a manner which is in itself known, byfiltering off the salt that has separated out, washing and neutralizingthe filtrate and drying it, evaporating the solvent, preferably underreduced pressure, and, if appropriate, freactionally distilling theresidue.

lt is, however, also possible, after adding the particular hydroxycompound, not to separate off the salt-like precipitate that hasseparated out but to add a mixture of the amine, solvent, andacid-binding agent after a certain time. The reaction mixture is thenworked up as described above.

The substances according to the invention are in most cases obtained inthe form of colorless to pale yellowcolored oils which sometimes cannotbe distilled without decomposition, but can however be freed of the lastvolatile constituents, and thus purified, by socalled slightdistillation", that is to say by prolonged heating under reducedpressure and at moderately elevated temperature. The substances arecharacterized, for example, by the refractive index. If theNMR-spectrum, the chromatogram or the elementary analysis shows thatnon-volatile impurities are contained in the product which has beensubjected to slight distillation, a separation from the impurities canfrequently be achieved by extracting the product with nonpolar solvents,for example petroleum ether.

As has already been mentioned, the new dichlorovinylthionophosphoricacid ester amides are distinguished by an outstanding insecticidal,above all soilinsecticidal, acaricidal and nematocidal activity towardsplant pests, pests harmful to health and storage pests, and towardsectoparasites. At the same time they possess a good action both againstsucking and against biting insects and mites (A Carina). Above all, theyare also active against those acarids which as animal extoparasitesattack domesticated animals. Furthermore, their good action againstparasitary fly larvae should be mentioned. At the same time they show alow phytotoxicity and, in some cases, also rodenticidal, fungicidal andbactericidal properties. The compounds according to the invention maytherefore be employed as pesticides, particularly in plant protectionand the protection of stored products, and also in the hygiene andveterinary fields.

To the sucking insects there belong, in the main, aphids (Aphididae)such as the green peach aphid (Myzus persicae), the bean aphid (Doralisfabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid(Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), thecurrant gall aphid (Cryptomyzus korschefu'), the rosy apple aphid(Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and thecherry black-fly (Myzus cerasi), in addition, sacles and mealybugs(Cocciria), for example the oleander scale (Aspidiotus hederae) and thesoft scale (Lecanium hesperidum) as well as the grape mealybug(Pseudococcus maritimus), thrips (Thysanoptera), such as Hercinothripsfemoralis. and bugs, for example the beet bug (Piesma quadrata), the redcotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), theassassin bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans)and, further, cicadas, such as Euscelis bilobarus and Nephotettixbipunctatus.

In the case of the biting insects, above all there should be mentionedbutterfly caterpillars (Lepidoptera) such as the diamond-back moth(Plutella maculipenm's), the gipsy moth (Lymantria dispar), thebrowntail moth (Euproctis chrysorrhoea) and tent caterpillar (Malacosomaneusm'a); further, the cabbage moth (Mamestra brassi'cae) and thecutworm (Agrotis segeturn), the large white butterfly (Pierisbrassicae), the small winter moth (Cheimarobia brumata), the green oaktortrix moth (Tortri'x viridana), the fall armyworm (Laphygmafragi'perda) and cotton worm (Prodem'a litura), the ermine moth(Hyponomeuta padella), the Mediterranean flour moth (Ephestia kuhniella)and greater wax moth (Galleria mellonella).

Also to be classed with the biting insects are beetles (Coleoptera), forexample the granary weevil (silo philus granarius Calandra granaria),the Colorado beetle (Leptinotarsa decemlineata), the dock beetle(Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), theblossom beetle (Meligethes aeneus), the raspberry beetle (Byturustomentosus), the bean weevil (Bruchidius Acanthoscelides obtectus), theleather beetle (Dermestes frischi), the khapra beetle (Trogodermagranarium), the flour be'etle (Tribolium castaneum), the northern cornbillbug (Calandra or Sitophilus zeamais), the drugstore beetle(Stegobium paniceum), the yellow mealworm (Tenebrio moliror) and thesaw-toothed grain beetle (Oryzaephilus surinamensis), but also speciesliving in the soil, for example wireworms (Agriotes spec.) and larvae ofthe cockchafer (Melolontha melolontha); cockroaches, such as the Germancockroach (Blattella germam'ca), American cockroach (Periplanetaamericana), Madeira cockroach (Leucophaea or Rhyparobi'a maderae),oriental cockroach (Blarra oriemalis), the giant cockroach (Blaberusgiganteus) and the black giant cockroach (Blaberus fuscus) as well asHenschoutedenia flexivitta; further, Orthoprera, for example the housecricket (Acheta domesticus); termites such as the eastern subterraneantermite (Reticulitermes flavipes) and Hymenoptera such as ants, forexample the garden ant (Lasius niger).

The Diptera comprise essentially the flies, such as the vinegar fly(Drosophila melanogaster), the Mediterranean fruit fly (Ceratitiscapitata), the house fly (Musca domestica), the little house fly (Fanniacanicularis), the black blow fly (Pharmia regina) and bluebottle fly(Calliphora erythrocephala) as well as the stable fly (Stomoxyscalcitrans); further, gnats, for example mosquitoes such as the yellowfever mosquito (Aedes aegvpti), the northern house mosquito (Culexpipiens) and the malaria mosquito (Anopheles stephensi).

With the mites (Acarina) there are classed, in particular, the spidermites (Tetranychidae) such as the twospotted spider mite (Tetranychusurticae) and the European red mite (Paratetranychus pilosus Panonychusulmi) gall mites, for example the black currant gall mite (Eriophyesribi's) and tarsonemids, for example the broad mite (Hemltarsonemuslatus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, suchas the relapsing fever tick (Ornithodorus moubata).

When applied against pests harmful to health and pests of storedproducts, particularly flies and mosquitoes, the compounds of thisinvention are also distinguished by an outstanding residual activity onwood and clay, as well as good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of thetype usable in conventional pesticide formulations or compositions, e.g.conventional pesticide dispersible carrier vehicles such as gases,solution,s emulsions, suspensions, emulsifiable concentrates, spraypowders, pastes, soluble powders, dusting agents, granules, etc. Theseare prepared in known manner, for instance by extending the activecompounds with con ventional pesticide dispersible liquid diluentcarriers and/or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g. conventional pesticide surface-activeagents, including emulsifying agents and/or dispersing agents, whereby,for example, in the case where water is used as diluent, organicsolvents may be added as auxiliary solvents. The following may bechiefly considered for use as conventional carrier vehicles for thispurpose: aerosol propellants which are gaseous at normal temperaturesand pressures, such as freon; inert dispersible liquid diluent carriers,including inert organic solvents, such as aromatic hydrocarbons (e.g.benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated,especially chlorinated aromatic hydrocarbons (e.g. chlorobenzenes,etc.), cycloalkanes (e.g. cyclohexane, etc.), paraffins (e.g. petroleumor mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g.methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol,ethanol, propanol, butanol, glycol, etc.) as well as ethers and estersthereof (eg glycol monomethyl ether, etc.), amines (e.g. ethanolamine,etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethylketone, methyl isobutyl ketone, cyclohexanone, etc), and/or water; aswell as inert dispersible finely divided solid carriers, such as groundnatural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e.calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.)and ground synthetic minerals (eg. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc.); whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents, for this purpose: emulsifying agents, suchas non-ionic and- /or anionic emulsifying agents (e.g. polyethyleneoxide esters of fatty acids, polyethylene oxide ethers of fattyalcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, etc., andespecially alkyl arylpolyglycol ethers, magnesium stearate, sodiumoleate, etc.); and/or dispersing agents, such as lignin, sulfite wasteliquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other acaricides,insecticides, fungicides, bactericides, nematocides and rodenticides, orherbicides, fertilizers, growth-regulating agents, etc., if desired orin the form of particular dosage preparations for specific applicationmade therefrom, such as solutions, emulsions, suspensions, powders,pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mix tures in which the active compoundis present in an amount substantially between about 0. l percent byweight, and preferably 05-90% by weight, of the mixture, whereas carriercomposition mixtures suitable for direct application of fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.000ll percent,preferably 0.011 percent, by weight of the mixture. Thus, the presentinvention contemplates over-all compositions which comprises mixtures ofa conventional dispersible carrier vehicle such as (1) a dispersibleinert finely divided carrier solid, and/or (2) a dispersible carrierliquid such as an inert organic solvent and/or water preferablyincluding a surface-active effective amount of a carrier vehicleassistant, e.g. a surface-active agent, such as an emulsifying agentand- /or a dispersing agent, and an amount of the active compound whichis effective for the purpose in question and which is generally betweenabout 0.0001-95 percent, and preferably 0.01-95 percent, by weight ofthe mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about to 1000 g/hectare, preferably 40 to600 g/hectare, are sufficient. ln this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about to about 95 percent by weight of theactive compound or even the 100 percent active substance alone, e.g.about 20-100 percent by weight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. insects, acarids,nematodes, rodents, fungi and bacteria and more particularly methods ofcombating at least one of insects, acarids and nematodes, whichcomprises applying to at least one of correspondingly (a) such insects,(b) such acarids, (c) such nematodes, (d) such rodents, (e) such fungi,(f) such bacteria, and (g) the corresponding habitat thereof, i.e. thelocus to be protected, a correspondingly combative or toxic amount, i.e.an insecticidally, acaricidally, nematocidally, rodenticidally,fungicidally or bactericidally effective amount, of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner. for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, squirting, sprinkling,pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The following examples are set forth to illustrate, without limitation,the process for producing the activc compounds according to the presentinvention.

EXAMPLE l a. The O-(2.2-dichlorovinyll-thionophosphoric acid esterdichloride required as the starting material can,

for example, be prepared as follows:

33 g of phosphorus(V) sulfide are added to 115 g ofO-(2,2dichl0rovinyl)-phosphoric acid ester dichloride in 170 g ofphosphorus sulfochloride and the mixture is heated to the boil underreflux. When the phosphorus(\/) sulfide has dissolved (0.5 to 1.5hours), the batch is cooled and the solution is decanted from theinsoluble matter. The phosphorus sulfochloride is distilled off and theresidue is distilled through a column. 84 g (68.3% of theory) of thedesired O-(2,2- dichlorovinyl)-thionophosphoric acid ester dichloride ofboiling point C/3 mm Hg and refractive index n of 1.5490 are thusobtained. b.

CH,NH

12.5 g of absolute ethanol and 26 g of triethylamine, dissolved in ml ofbenzene, are added dropwise, at 5 to 10C, to a solution of 61.5 g (0.25mole) of O- (2,2-dich1orovinyl)-thionophosphoric acid ester dichloridein 300 ml of benzene. After completion of the dropwise addition, thebatch is stirred for 1.5 hours at 40C and then cooled to 10C.Methylamine is passed into the cold solution until it reacts alkaline,and the batch is stirred for a further half-hour at 10C and a furtherhour at 30 to 40C. Thereafter, the salt which has precipitated isfiltered off, the filtrate is concentrated under reduced pressure, theoily residue which remains is taken up in methylene chloride, and themethylene chloride solution is washed with water and dried. Afterdistilling off the solvent, an oil remains, which can be distilledwithout decomposition. 47 g (75% of theory) of the desiredO-ethyl-O-(2,2-dichlorovinyl)-H-methylthionophosphoric acid ester amideof boiling point l28138C/6 mm Hg and a refractive index n of 1.5l11 areobtained. Calculated for c ri ci ivows (molecular weight 250.04)

Cl N P S 28.4%; 5.6%; 12.4%. l2.8% Found. 28.5%; 5.8%; 12.7% [2.6%.

EXAMPLE 2 S [CH;,l;CHO ll 20.5 g of isopropanol and 34 g oftriethylamine, dissolved in 100 ml of benzene, are added dropwise to asolution, cooled to 5l0C, of 82 g (0.33 mole) of O-(2.2-dichlorovinyl)-thionophosphoric acid ester dichloride in 300 ml ofbenzene. The batch is stirred for one hour at 40C and is then cooled to20C. At this temperature, a solution of 21 g of isopropylamine and 34 gof triethylamine in 100 ml of benzene is added dropwise to the reactionmixture and the latter is stirred for 2 hours at 40C. Thereafter thesalts which has separated ot is filtered off, the filtrate isconcentrated under reduced pressure, the oil which remains is taken upin methylene chloride and the methylene chloride solution is washeduntil it reacts neutral, and dried. After stripping off the solvent, anoil is obtained, which is distilled in order to purify it. 62 g (63.5%of theory) ofO-isopropyl-O-(2,2-dichlorovinyl)-N-isopropyl-thionophosphoric acidester amide of boiling point 102C/0.01 mm Hg and a refractive index n of1.5118 are obtained. Calculated for C H CI NO PS (molecular weight292.17)

c1 N P s 24.27%; 4.79%; 10.60%; 10.97% Found: 24.90%; 4.72%; 10.98%;12.09%.

EXAMPLE 3 s CH,CH,-CH,O ll

P ocH=cc1, (3) (cH,),N

A solution, cooled to C, of 300 ml of benzene and 82 g (0.33 mole) ofO-(2,2-dichlorovinyl)-thionophosphoric acid ester dichloride is treateddropwise with 48 g of 3-cyclohexyll -propanol and 34 g of triethylamine,dissolved in 50 ml of benzene. Thereafter the batch is stirred for ahalf-hour at 40C and then cooled to 10C. 16 g of dimethylamine and 34 gof triethylamine in 200 ml of benzene are added dropwise to the coldsolution. In order to achieve complete conversion, the batch is stirredfor a further hour at 40C. The salt which has separated out is filteredoff, the filtrate is washed with water and subsequently dried, andthereafter the solution is concentrated under reduced pressure andsubjected to slight distillation". The product which has been subjectedto distillation is extracted with petro- EXAMPLE 4 31 g of n-propanoland 40 g of pyridine, dissolved in 100 ml of methylene chloride, areadded dropwise at 20C to a solution of 123 g (0.5 mole) of O-(2,2-dichlorovinyl)-thion0phosphoric acid ester dichloride in 400 ml ofmethylene chloride at 20C. After completion of the dropwise addition,the batch is further stirred for 1.5 hours at 40C. It is then cooled to10C and dimethylamine is passed in until the mixture reacts alkaline. Tocomplete the reaction, the mixture is further stirred for a half-hour at10C and another hour at to C. The salt which has separated out isfiltered off and the filtrate is concentrated to half under reducedpressure. It is washed once with very dilute hydrochloric acid, oncewith a very dilute sodium hydroxide solution and twice with water.Finally, the batch is dried over sodium sulfate. After filtering off thedrying agent and concentrating the solution, an 01] remains, which canbe distilled. The yield is 78 g (56% of thecry) ofO-propyl-O-(2,2-dich1orovinyl)-N,N-dimethylthionophosphoric acid esteramide of boiling point 130l35C/12 mm Hg and refractive index n of1.4930.

Calculated for C,H,,Cl NO PS (278.14)

30 lcum ether and the extract is concentrated. A light yellow oil with arefractive index n of l .5062 is left. The CI N p 5 yield is 69 g (57.5%of theory). Calculated for 25.5%; 5.0%; 11.1%; 11.5% c,,H,,c1,No,1 s"1616611161 weight 360.28): Fmmd- 213% 4 4% 114% N P S 35 Th r 11 d[963%. 189%; 860%; 890% e o owmg compoun s are prepared 1n a mannerFound: 19.49%; 3.68%; 8.54%; 8.58%. analogous to that described inExamples 1 t0 4:

OR c1.c=cH o P R, 111

Cpd. R R. R, 11,, vi w of theory} 5 CH H CH 1.5189 54 6 CH, H C,H,1.5118 5| 7 CH, H "-43.11, 1.5088 63.5 8 CH, H 1 C,H,. 1.5009 70.5 9 CH,H CH,=CH CH, 1.5231 54 10 CH, H n C.H. 1.5081 11 CH, H i-C.H. 1.5039 5912 C,H, H n c,H 1.4990 71 13 C,H H 1-C,H 1.4942 48.5 14 Cm, H CH,=CH CH,1.5112 71 15 C,H, H n c,H, 1.4963 74 16 C,H, H i-C ,H, 1.4970 45 17 C,H,H sec.C.H, 1.4930 71 1a C,H, C,H c,H 1.4900 45 19 C,H n-C H n-C;,H-,1.4930 42 20 C,H, H CH,0 CH,CH,CH 1.5022 55.5 2 C,H, H CH,o CH,CH,1.4979 49 22 C,H H C,H,0-CH,CH,CH, 1.4995 51 23 C,H, CH,=CHCH, CH,=CHCH, 1.5042 64.5 24 C,H (CH,),- 1.5142 63 25 Cm, (CH,). 1.5174 59 26 C,H(CH,),O-(CH, 1.5126 27 n c,H, H CH 1.5028 63.5 28 n-C ,H, H n c H,1.4962 29 11-C,H H i c,H, 1.4933 68 30 n-C H H CH,=CH CH 1.5039 68.5 31n C,H, H n c.H, 1 .4951; 67.5 11-C,H H i-C.,H, 1.4913 71.5 32 33 11 C,HH scc.-C,H. 1.4918 66.5 34 n C,H, C,H C,H, 1.4889 61.0 35 1 c,H, H CH1.5107 71.5 36 i-C,H, H CH,=CH CH, 1.5165 76.5 37 Br-CH,-*CH, H CH,1.5470 81 -continued II 0R c1,C=cH 0 P R. m

Cpd. R R, R, N t Yield {'52 of theory] 100 CH,CH R CH,=CH CH, 1.5492 as101 O CH,CH,CH H CH 1.5475 77.5

102 CH,CH,CH, H i C,H, 1.5500 88 103 CH,CH,CH, H CH,=CH-CH, 1.5454 84.5

104 (CHJhC H CH3 1.5472 37 s (CHmC H i-C,H7 1.5375 86 100 (CHmC H CH,=CHCH, 1.5445 85 107 1 C.H, CH, CH, 1.4920 71; 10s n-C.H., CH CH, 1.49096L5 109 CH: CH, 1.5532 71 1 10 sec.C H, CH: CH, 1.4949 59 111 n-C.H. CH;CH, 1.4922 155.5 1 12 1:.Hs CH, CH, 1.4970 so 113 c,H H c,H, 1.5349 57.51 14 1:..,H.l H H,

1 1 C,H, H c,H. 1.4962 7s 1 10 1-C.1-1. H C,H, 1.4920 74 The unexpectedsuperiority and outstanding activity of the particular new compounds ofthe present invention are illustrated, without limitation. by thefollowing examples. In some instances the compounds indicated as known"might not actually have been shown in the art but perform similarly toother compounds actually disclosed in the art.

EXAMPLE 5 Drosophila test Solvent: 3 parts by weight acetone Emulsifier:1 part by weight alkylarylpolyglycol ether To produce a suitablepreparation of active com mixed with the stated amount of solventcontaining the stated amount of emulsifier, and the concentrate isdiluted with water to the desired concentration.

1 cc of the preparation of the active compound is applied with a pipetteto a filter paper disc of 7 cm of diameter. The wet disc is placed in aglass vessel containing 50 vinegar flies (Drosophila melanogaster) andcovered with a glass plate.

After the specified periods of time, the destruction is determined as apercentage: I00 percent means that all the flies are killed; 0% meansthat none of the flies are killed.

The active compounds, their concentrations, the evaluation times and thedegree of destruction can be pound, 1 part by weight of the activecompound is seen from Table 2:

Table 2 (Drosophila Test) Active compound Concentration of Degree ofactive compound Destruction in in after 1 day 0 CH,O ll 0.0001 POCH=CC|(A) 0.0000l 0 CH,,O

(known) S CH,0

POCH=CCl, (5) 0.000l 100 CH -NH 0.0000] 100 Cd-h-NH Table 2-continued(Drosophila Test) Active compound Concentration of Degree of activecompound Destruction in in b after day S C,H,O ll 00001 100 POCH=CC1,0.00001 C H,-NH

(known) CH,

CH-O ll CH, POCH=CC1, 0.0001 100 0.00001 100 EXAMPLE 6 Myzus test(contact action) Solvent: 3 parts by weight acetone Emulsifier: 1 partby weight alkylaryl polyglycol ether To produce a suitable preparationof active compound, 1 part by weight of the active compound is mixedwith the stated amount of solvent containing the stated amount ofemulsifier and the concentrate is diluted with water to the desiredconcentration.

Table 3 (Myzus Test) Active compound Concentration of Degree of activecompound destruction in in I: after 1 day CH,0 0.1 100 P0-CH=CC1, 0.01000 0.001 0 (known) (A) CH,0CH,--CH,O S

H 0.1 100 P-OCH=CC1, 0.01 100 0.001 CH,NH

(64) C,H,O-CH,CH,O S

H 001 P-OCH=CC1, 0.01 100 0001 99 CH,NH

C,H10CH,CH,O S

\ II 0.1 100 P0CH=CC1, 0.01 99 0.001 85 CH,-NH

C,H,OCH,CH,O S

It 0.1 100 POCH=CC1, 0.01 100 0.001 99 CH,NH

2) (CH,),CHCH,-CH,O S

H 0.1 100 P-0CH=CC1, 0.01 100 0.001 70 CH -NH (47) (C,H,),CHCH,O S

H 0.1 100 POCH= CC1 0.01 99 0.001 55 CH:NH

\ II 0.1 100 P0-CH=CC1, 0.01 100 2 l 22 Table 3-continued (Myzus Test)Active compound Concentration of Degree of active compound destructionin in after 1 day u 0.1 100 POCH=CCI, 0.01 98 CH,=CHCH,-NH

(7 C H -O S II 0.1 50 P-O-CH-CCl, 0.01 O C.H.-NH

(known) (D) CH,

cH-o s 1| 0.1 100 CH, P- CH=CCI, 0.01 98 c,H.-NH

cH-cH, o s cH, 11 0.1 100 PO-CH=CCI, 0.0] [00 CgHg-NH (1 l6) EXAMPLE 7of approximately l0-30 cm., are sprayed with the prep- Tetranychustest/resistant Solvent: 3 parts by weight acetone Emulsifier: I part byweight alkylaryl polyglycol ether To produce a suitable preparation ofactive compound, l part by weight of the active compound is mixed withthe stated amount of solvent containing the stated amount of emulsifierand the concentrate so obtained is diluted with water to the desiredconcentratron.

Bean plants (Phaseolus vulgaris), which have a height aration of theactive compound until dripping wet. These bean plants are heavilyinfested with spider mites (Tetranychus urticae) in all stages ofdevelopment.

After the specified periods of time, the effectiveness of thepreparation of active compound is determined by counting the dead mites.The degree of destruction thus obtained is expressed as a percentage:I00 percent means that all the spider mites are killed whereas 0 percentmeans that none of the spider mites are killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following Table 4:

Table 4 Active compound (Terranychus Test) Concentration of activecompound Degree of destruction in in I; after 8 days cr1,o u

' \PO-CH=CCI, 0.1 20 cH,o 0.01 0 (known) (A) s CH,O\ 11 0.1 98

P o CH=CCl CH, NH

79) s 0.1 100 cH,o-cH,-cr1,0 0.01

1= 0 crr==cc|, cm-NH (6 s 0.1 c,H,o cH, cH,o n 0.01 50 P-0CH=CCI, CH NH0.1 100 C,H,OCH,-CH,O 1| 0.01 so P O CH=CCI, CH,-NH

0.1 100 c.1i.o c|-1, cH,0 0.01 91;

Table 4-continued Temmychu: Tell) Active compound active compoundConcentration of Degree of destruction in in I: I: after 8 days DJ 98040i Oil I00 EXAMPLE 8 emulsifier is added and the concentrate isdiluted with water to the desired concentration.

The preparation of active compound is intimately mixed with soil whichis heavily infested with the test nematodes. The concentration of theactive compound in the preparation is of practically no importance; onlythe amount of active compound per unit volume of soil, which is given inp.p.m., is decisive. The soil is filled into pots, lettuce is sown inand the pots are kept at a greenhouse temperature of 27C. After 4 weeks,the lettuce roots are examined for infestation with nematodes, and thedegree of destruction of the active compound is determined as apercentage. The degree of effectiveness is percent when infestation iscompletely avoided; it is 0 percent when the infestation is exactly thesame as in the case of the control plants in untreated soil which hasbeen infested in the same manner.

The active compounds, the amounts applied and the results can be seenfrom the following Table 5:

Table 5-continued (Meloidogyne incogm'm Test) Active compound Degree ofdestruction in k for an active compound concentration of 20 10 5 2.5[.25 0,625 ppm C H.O O ll POCH=CCI, 0 (CH=)1 (G) (known) CH|0 0 ll POCH=CCl 0 ((3H,),CH-NH (H) (known) P0CH=CCI, 0

CHaCH-CH NH (K) (known) CH,0CH,CH O

POCH=CCI, 0

(CH:)1CHNH (L) (known) C,H.O 0 U OCH=CCl, 0

CH N a): (known) CH,-CH,CH O \fi cH=cc1, 0

CH, NH

(N) (known) CH,-CH.CH,-CH,O 0 ll P0CH=*CCI; CH,NH

(P) (known) C,H OCH,CH,O 0 ll OCh==CCl, 0

CH,NH

(0) (known) CJ-h-O S ll -0CH=CCI, 0

CJL-NH (D) (known) CH-O CH,

O-CH=CCI, I00 C,H.NH

CH-CHg-O CH,

POCH=CCI, I00

EXAMPLE 9 Table 6 weight of active compound per unit volume of soil,which is given in p.p.m. (for example mg/l), is decisive. The soil isfilled into pots and the pots are left to stand at room temperature.After 24 hours, the test insects are put into the treated soil and,after a further 48 hours, the degree of effectiveness of the activecompound is determined as a percentage by counting the dead and livingtest insects. The degree of effectiveness is 100 percent when all thetest insects have been killed; it is 0 percent when exactly as many testinsects are still alive as in the case of the control.

The active compounds, the amounts applied and the results can be seenfrom the following Table 6:

(Tenebn'o molr'tor larvae in the soil) Active compound Degree ofdestruction in '70 for an active compound concentration of l0 s 2.5 1.250.625 ppm fi I00 too [00 mt) so 0 Q ocH=cc|, cH.-NH

s 100 95 so cH,o H O -ocH==cc1,

Clh-NH 100 100 I00 100 I00 I00 (cH.),cH-cu.-cH, o fi ocH=cc|, CH,-NH(47) S 100 I00 I00 I00 100 95 CH-O P-oc|-i=cc|,

CH,NH

s c,H,- H-O 100 I00 I00 50 P-ocH=cc|, (CH,),CHNH/ o fi too too I00 100100 P-0CH=CCl, CH,-NH

s E I00 I00 lOO I00 I00 so -ocH=cc|, CH,--NH

P-ocH=-cc|, 100 I00 90 so CH,=CH-CH,-NH

(75) s (cH.),cH o I00 I00 98 so P ocH=ccx, (CHflzCH-NH (2) s c," o u 100100 I00 I00 so a -OCH=CCI, CPL-NH (n S 100 CHO u I00 100 I00 I00 I00 I0CH=CCl.

(Tenebric) rrwfilur iarvac in \he soil) Degree of destruction in 7: foran 1.25 0.625 ppm active compound concentraziun of 20 1O 5 IOU Activecumpound

1. A DICHLOROVINYLTHIONOPHOSPHORIC ACID ESTER AMIDE OF THE FORMULA
 2. Adichlorovinylthionophosphoric acid ester amide according to claim 1selected from the group consisting of
 3. A dichlorovinylthionophosphoricacid ester amide according to claim 1 of the formula
 4. Adichlorovinylthionophosphoric acid ester amide according to claim 1 ofthe formula
 5. A dichloroVinylthionophosphoric acid ester amideaccording to claim 1 of the formula
 6. A dichlorovinylthionophosphoricacid ester amide according to claim 1 of the formula
 7. Adichlorovinylthionophosphoric acid ester amide according to claim 1 ofthe formula